EP2917179B1 - Verfahren zur herstellung von gleichgewichtsperessigsäure und mit dem verfahren erhältliche gleichgewichtsperessigsäure - Google Patents

Verfahren zur herstellung von gleichgewichtsperessigsäure und mit dem verfahren erhältliche gleichgewichtsperessigsäure Download PDF

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Publication number
EP2917179B1
EP2917179B1 EP13776762.0A EP13776762A EP2917179B1 EP 2917179 B1 EP2917179 B1 EP 2917179B1 EP 13776762 A EP13776762 A EP 13776762A EP 2917179 B1 EP2917179 B1 EP 2917179B1
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EP
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Prior art keywords
acid
weight
hydrogen peroxide
equilibrium peracetic
equilibrium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP13776762.0A
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German (de)
English (en)
French (fr)
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EP2917179A1 (de
Inventor
Andreas Reinold
Stefan Leininger
Angela HELLWIG
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Evonik Operations GmbH
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Evonik Degussa GmbH
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Priority to EP13776762.0A priority Critical patent/EP2917179B1/de
Priority to PL13776762T priority patent/PL2917179T3/pl
Priority to SI201331132T priority patent/SI2917179T1/sl
Publication of EP2917179A1 publication Critical patent/EP2917179A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C409/00—Peroxy compounds
    • C07C409/24—Peroxy compounds the —O—O— group being bound between a >C=O group and hydrogen, i.e. peroxy acids
    • C07C409/26—Peracetic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds

Definitions

  • the invention relates to a process for the preparation of equilibrium peracetic acid and obtainable by the process equilibrium peracetic acid low corrosivity.
  • Peroxyacetic acid is used as a disinfectant, which already at low temperatures has a broad effect against bacteria and other microorganisms, as well as against viruses and against which bacteria and viruses do not resist.
  • Peroxyacetic acid has the advantage that at the application concentrations that are used for disinfection, after a time complete hydrolysis to acetic acid and hydrogen peroxide takes place, so that the biocidal effect is lost and it can not lead to an accumulation of biocide.
  • Peroxyacetic acid is usually marketed in the form of equilibrium peracetic acid, which is brought to the desired concentration of use for application with water.
  • equilibrium peracetic acid is a mixture which contains peroxyacetic acid, hydrogen peroxide, acetic acid and water in chemical equilibrium.
  • the chemical equilibrium is established between these four components according to the following reaction equation: CH 3 C (O) OH + H 2 O 2 ⁇ CH 3 C (O) OOH + H 2 O
  • Equilibrium peracetic acid is usually prepared from acetic acid and aqueous hydrogen peroxide solution by adjusting this equilibrium. The adjustment of the balance takes place in the absence of other components, however, only slowly and requires at 20 ° C for several days. To accelerate the adjustment of the equilibrium therefore usually sulfuric acid is added as a catalyst. Addition of larger amounts of sulfuric acid also allows in disinfection applications to control the metered amount of peroxyacetic acid through the conductivity of the disinfecting solution.
  • Equilibrium peracetic acid containing sulfuric acid has the disadvantage that it has a corrosive effect on metallic materials and that it can not be stored in contact with stainless steel, since iron ions dissolved out of the material catalyze the decomposition of peroxyacetic acid.
  • JP 10-330357 describes a preparation of peroxyacetic acid by reacting butyl acetate with 60 wt .-% hydrogen peroxide solution with the addition of methanesulfonic acid as a catalyst. The reaction in the absence of a carboxylic acid corrosion problems should be avoided.
  • the utility model DE 20 2007 005 732 U1 describes a cleaning agent for removing solid deposits in drinking water pipes containing 1 to 14% by weight of sulfamic acid, 5 to 10% by weight of methanesulfonic acid, 0.075 to 0.15% by weight of phosphonobutane tricarboxylic acid, 0.3% by weight of 2-propanol and contains 100% supplementary water.
  • the detergent can be provided by adding 1 to 10 wt .-% disinfectant with a disinfecting effect, which can be used as disinfectant hydrogen peroxide-containing substances such as peracetic acid.
  • compositions for the dissolution of oxalate deposits containing methanesulfonic acid and additionally phosphoric acid or nitric acid may contain one or more additives, among others, as disinfectants, bromoacetic acid, peracetic acid, salicylic acid and hydrogen peroxide.
  • the invention therefore provides a process for the preparation of equilibrium peracetic acid by reacting acetic acid with hydrogen peroxide in an aqueous reaction mixture, the reaction being carried out in the presence of methanesulfonic acid as the catalyst.
  • the invention also provides the use of methanesulfonic acid as catalyst for the preparation of equilibrium peracetic acid from acetic acid and hydrogen peroxide.
  • Another object of the invention is an equilibrium peracetic acid comprising peroxyacetic acid, hydrogen peroxide, acetic acid and water and containing methanesulfonic acid.
  • acetic acid and hydrogen peroxide are reacted in aqueous reaction mixture in the presence of methanesulfonic acid to give equilibrium peracetic acid.
  • Methanesulfonic acid acts as a catalyst, which increases the rate of reaction of acetic acid with hydrogen peroxide to peroxyacetic acid.
  • the reaction is preferably carried out until the content of peroxyacetic acid has reached more than 90% and more preferably more than 95% of the content present in the chemical equilibrium.
  • the reaction mixture for the reaction of acetic acid with hydrogen peroxide contains 0.1 to 2.0% by weight of methanesulfonic acid, more preferably 0.5 to 2.0% by weight of methanesulfonic acid.
  • the reaction mixture for the reaction of acetic acid with hydrogen peroxide contains from 5 to 30% by weight of methanesulfonic acid.
  • methanesulfonic acid in this concentration range, an equilibrium peracetic acid can be obtained whose dosage for disinfection applications can be controlled by the electrical conductivity of the dilute solution and which has a substantially lower corrosive action than an equilibrium peracetic acid containing suitable amounts of sulfuric acid for the same purpose Has metals.
  • the heat development in the reaction mixture is significantly lower than when using an appropriate amount of sulfuric acid.
  • acetic acid can be used in pure form or in the form of an aqueous solution.
  • acetic acid is used in pure form.
  • Hydrogen peroxide is preferably used in the form of an aqueous solution with a content of 10 to 85 wt .-%, particularly preferably 25 to 60 wt .-%.
  • water may optionally be added to the reaction mixture.
  • the aqueous reaction mixture contains no additional solvent besides water.
  • the amounts of acetic acid, hydrogen peroxide and water in the reaction mixture are chosen so that after equilibration the desired content of peroxyacetic acid and hydrogen peroxide in the equilibrium peracetic acid is achieved.
  • Acetic acid and hydrogen peroxide are preferably used in a molar ratio in the range of 0.5 to 10, particularly preferably 0.5 to 5.
  • Methanesulfonic acid is used for the process according to the invention preferably in pure form or in the form of an aqueous solution, more preferably in the form of an aqueous solution containing from 1 to 40% by weight of water.
  • the reaction mixture is prepared by mixing acetic acid, aqueous hydrogen peroxide solution containing from 25 to 60% by weight of hydrogen peroxide and methanesulfonic acid, wherein the methanesulfonic acid may contain from 1 to 40% by weight of water.
  • acetic acid, hydrogen peroxide and methanesulfonic acid are added to the reaction mixture.
  • Methanesulfonic acid is preferably added after mixing acetic acid and hydrogen peroxide or added to one of the starting materials acetic acid or aqueous hydrogen peroxide solution.
  • the methanesulfonic acid is added to the hydrogen peroxide solution.
  • acetic acid and aqueous hydrogen peroxide solution can be mixed batchwise with one another in the process according to the invention.
  • acetic acid and aqueous hydrogen peroxide solution may also be mixed continuously, for example via a static mixer.
  • a continuous mixing the in WO 02/26459 described methods are used.
  • conversion to equilibrium peracetic acid can be made in any container. Since the heat of reaction of the Reaction is low, the reaction can be carried out without cooling and even adiabatic. In a preferred embodiment, the reaction takes place after mixing in a storage container or transport container for equilibrium peracetic acid.
  • the equilibrium peracetic acid obtainable by the process of the present invention includes peroxyacetic acid, hydrogen peroxide, acetic acid, water and methanesulfonic acid.
  • Peroxyacetic acid, hydrogen peroxide, acetic acid and water are in chemical equilibrium.
  • the equilibrium peracetic acid according to the invention preferably contains from 2 to 24% by weight, more preferably from 3 to 17% by weight and in particular from 4 to 15% by weight, of peroxyacetic acid.
  • the equilibrium peracetic acid of the present invention contains from 2 to 12% by weight of peroxyacetic acid and from 5 to 30% by weight of methanesulfonic acid and the weight ratio of methanesulfonic acid to peroxyacetic acid is in the range of 2 to 5.
  • diluting the equilibrium peracetic acid may be based on Application concentration for disinfection applications can be controlled by the electrical conductivity of the diluted solution.
  • the equilibrium peracetic acid according to the invention contains, in addition to peroxyacetic acid, hydrogen peroxide, acetic acid, water and methanesulfonic acid, up to 5% by weight of one or more surfactants.
  • Suitable surfactants for use in equilibrium peracetic acid are known in the art, for example DE 26 16 049 A1 . EP 147 207 . WO 93/10088 .
  • Preferred surfactants are anionic surfactants, such as alkyl sulfonates, alkyl sulfates and alkylbenzenesulfonates, and nonionic surfactants, such as fatty alcohol alkoxylates, fatty acid alkoxylates and tertiary amine oxides having a long-chain alkyl radical.
  • anionic surfactants such as alkyl sulfonates, alkyl sulfates and alkylbenzenesulfonates
  • nonionic surfactants such as fatty alcohol alkoxylates, fatty acid alkoxylates and tertiary amine oxides having a long-chain alkyl radical.
  • the equilibrium peracetic acid according to the invention may additionally contain one or more stabilizers which stabilize peroxyacetic acid against catalytic decomposition by heavy metal ions.
  • Suitable stabilizers for peroxyacetic acid are known in the art, for example EP 742 206 B1 , Paragraphs [0016] and [0017].
  • Preferred stabilizers are 1-hydroxyethane-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetra (methylenephosphonic acid), dipicolinic acid and their alkali metal salts.
  • the equilibrium peracetic acid according to the invention may additionally contain one or more hardness-stabilizing compounds which can complex calcium and magnesium ions.
  • Suitable hardness-stabilizing compounds for equilibrium peracetic acid are known from the prior art, for example from EP 945 405 B1 , Paragraph [0005].
  • a polymer containing carboxyl groups is used as the hardness-stabilizing compound.
  • polymers from the series (i) by oxidative polymerization of acrolein or acrolein and acrylic acid produced polymers, (ii) polyacrylic acid, (iii) copolymers of acrylic acid and another unsaturated carboxylic acid, especially maleic acid, and (iv) polymaleic acid, wherein the average molecular weight Mw of the polymer is in the range of 500 to 25,000, in particular 1,000 to 15,000. In of equilibrium peracetic acid, carboxyl groups of the hardness-stabilizing polymer may be partially converted into percarboxylic groups.
  • the equilibrium peracetic acid according to the invention contains less than 1% by weight of additional compounds besides peroxyacetic acid, hydrogen peroxide, acetic acid, water, methanesulfonic acid, optionally up to 5% by weight of surfactants and optionally up to 10% by weight of polymers containing carboxyl groups.
  • the equilibrium peracetic acid formed contained 15.2% by weight of peroxyacetic acid, 14.3% by weight.
  • Hydrogen peroxide and 0.7 wt .-% methanesulfonic acid for this equilibrium peracetic acid, a self-accelerating decomposition temperature (SADT) of 50 ° C. for storage in a non-isolated test specimen UN H.2 for hazardous goods of UN class 5.2 was used in a 1 liter spherical autoclave with the addition of a pickled metal coupon 17.5 m 3 stainless steel tank determined.
  • the UN Class 5.2 hazardous goods UN H.2 test method in a 1 l sample overadiabatic storage and two 20 * 60 * 2 mm HDPE plates in a 1 l spherical dewar became a self-accelerating decomposition temperature (SADT) of 70 ° C for storage in a 1 m 3 HDPE IBC.
  • SADT self-accelerating decomposition temperature
  • Example 8 1141.0 g of PERSYNTH® 500LC hydrogen peroxide 49.4% by weight, 567.6 g of acetic acid, 269.9 g of deionized water, 19.8 g of 98% by weight of sulfuric acid, 1.6 g of 1- Hydroxyethane-1,1-diphosphonic acid and 0.24 g of pyridine-2,6-dicarboxylic acid and reacted by standing at room temperature to equilibrium peracetic acid.
  • the resulting equilibrium peracetic acid contained 14.5% by weight of peroxyacetic acid, 21.4% by weight of hydrogen peroxide and 1.0% by weight of sulfuric acid. 3 parts of the equilibrium peracetic acid were diluted with 997 parts of demineralized water to a disinfecting solution.
  • the disinfecting solution thus obtained was stored at room temperature in contact with a material coupon (steel material number 1.0038 with the dimensions 60 * 20 * 3 mm), which was previously pickled for 1 h at 20 ° C with inhibited hydrochloric acid. After 24 h, the material coupon was clearly rusty and the solution discolored yellowish, the content of peroxyacetic acid had decreased to 2 ppm (determined with Merck Reflectoquant® test strips). From the weight decrease of the material coupon, a material removal of 0.4 mm / a was calculated. Without material coupon, the content of peroxyacetic acid after 24 h at 380 ppm and after 72 h at 370 ppm (colorimetrically determined with ABTS color reagent).
  • Example 9 Example 8 was repeated, but instead of the sulfuric acid, 28.6 g of 70% by weight of methanesulfonic acid Lutropur MSA from BASF were used and the amount of deionized water was reduced to 261.2 g.
  • the resulting equilibrium peracetic acid contained 14.6% by weight of peroxyacetic acid, 21.6% by weight of hydrogen peroxide and 1.0% by weight of methanesulfonic acid.
  • the disinfectant solution prepared by dilution showed no discoloration on storage in contact with the material coupon and no change was visible on the material coupon after 72 hours. From the weight decrease of the material coupon a material removal of less than 0.01 mm / a was calculated.
  • Example 10 1052.7 g of 49.4% by weight of PERSYNTH® 500LC hydrogen peroxide, 160.1 g of acetic acid, 479.7 g of deionized water, 306.2 g of 98% by weight of sulfuric acid, 1.4 g of 11- Hydroxyethane-1,1-diphosphonic acid and 0.18 g of pyridine-2,6-dicarboxylic acid and reacted by standing at room temperature to equilibrium peracetic acid.
  • the resulting equilibrium peracetic acid contained 5.0% by weight of peroxyacetic acid, 23.7% by weight of hydrogen peroxide and 15.0% by weight of sulfuric acid. 1 part of the equilibrium peracetic acid was diluted with 99 parts of demineralized water to a disinfecting solution.
  • the disinfecting solution thus obtained was stored in contact with a material coupon as in Example 8. After 15 minutes, the material coupon was clearly rusty, the solution was yellow discolored after 24 h and cloudy, the content of peroxyacetic acid had decreased to 7 ppm (determined with Merck Reflectoquant® test strips). From the weight decrease of the material coupon a material removal of 8 mm / a was calculated. Without Material coupon was the content of peroxyacetic acid after 24 h at 370 ppm (determined colorimetrically with ABTS color reagent).
  • Example 10 Example 10 was repeated, but instead of the sulfuric acid, 428.7 g of 70% by weight of methanesulfonic acid Lutropur MSA from BASF were used and the amount of deionized water was reduced to 357.3 g.
  • the resulting equilibrium peracetic acid contained 4.7% by weight of peroxyacetic acid, 23.9% by weight of hydrogen peroxide and 15.0% by weight of methanesulfonic acid.
  • the disinfectant solution prepared by dilution showed no discoloration or haze after 48 h of storage in contact with the material coupon, and no change was visible on the material coupon after 48 h. From the weight decrease of the material coupon, a material removal of 2.7 mm / a was calculated.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Engineering & Computer Science (AREA)
  • Detergent Compositions (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Pyrane Compounds (AREA)
EP13776762.0A 2012-11-08 2013-10-09 Verfahren zur herstellung von gleichgewichtsperessigsäure und mit dem verfahren erhältliche gleichgewichtsperessigsäure Active EP2917179B1 (de)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP13776762.0A EP2917179B1 (de) 2012-11-08 2013-10-09 Verfahren zur herstellung von gleichgewichtsperessigsäure und mit dem verfahren erhältliche gleichgewichtsperessigsäure
PL13776762T PL2917179T3 (pl) 2012-11-08 2013-10-09 Sposób wytwarzania kwasu nadoctowego w stanie równowagi i otrzymywany tym sposobem kwas nadoctowy w stanie równowagi
SI201331132T SI2917179T1 (sl) 2012-11-08 2013-10-09 Postopek priprave ravnotežne perocetne kisline in ravnotežna perocetna kislina, pridobljena po tem postopku

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP12191799 2012-11-08
EP13776762.0A EP2917179B1 (de) 2012-11-08 2013-10-09 Verfahren zur herstellung von gleichgewichtsperessigsäure und mit dem verfahren erhältliche gleichgewichtsperessigsäure
PCT/EP2013/071013 WO2014072143A1 (de) 2012-11-08 2013-10-09 Verfahren zur herstellung von gleichgewichtsperessigsäure und mit dem verfahren erhältliche gleichgewichtsperessigsäure

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EP2917179A1 EP2917179A1 (de) 2015-09-16
EP2917179B1 true EP2917179B1 (de) 2018-06-20

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US (1) US9573893B2 (ja)
EP (1) EP2917179B1 (ja)
JP (1) JP6104397B2 (ja)
KR (1) KR102158059B1 (ja)
CN (1) CN104684892B (ja)
AR (1) AR093406A1 (ja)
AU (1) AU2013343772B2 (ja)
BR (1) BR112015007192B1 (ja)
CA (1) CA2890831C (ja)
ES (1) ES2684224T3 (ja)
HK (1) HK1210138A1 (ja)
MA (1) MA20150407A1 (ja)
PL (1) PL2917179T3 (ja)
PT (1) PT2917179T (ja)
SI (1) SI2917179T1 (ja)
TW (1) TWI603952B (ja)
UY (1) UY35124A (ja)
WO (1) WO2014072143A1 (ja)
ZA (1) ZA201503136B (ja)

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CN103704264B (zh) * 2014-01-09 2016-04-20 南通思锐生物科技有限公司 一种消毒清洁剂
CN104304315A (zh) * 2014-09-18 2015-01-28 魏巍 一种稳定的低腐蚀性杀孢子剂及其制备方法
US9907305B2 (en) 2016-03-22 2018-03-06 Solvay Sa Production of disinfecting solutions
AU2020282801B2 (en) * 2019-05-31 2023-09-28 Ecolab Usa Inc. Method of monitoring peracid concentrations by conductivity measurements and peracid composition
KR20230027624A (ko) * 2021-08-19 2023-02-28 주식회사 휴온스메디텍 살균소독용 과아세트산 조성물 및 이의 제조방법

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Publication number Publication date
US9573893B2 (en) 2017-02-21
UY35124A (es) 2014-06-30
KR20150081280A (ko) 2015-07-13
EP2917179A1 (de) 2015-09-16
CA2890831A1 (en) 2014-05-15
JP2015535297A (ja) 2015-12-10
TWI603952B (zh) 2017-11-01
MA20150407A1 (fr) 2015-11-30
ES2684224T3 (es) 2018-10-01
SI2917179T1 (sl) 2018-09-28
AR093406A1 (es) 2015-06-03
CN104684892B (zh) 2017-08-29
TW201431835A (zh) 2014-08-16
CN104684892A (zh) 2015-06-03
BR112015007192A2 (pt) 2017-07-04
PL2917179T3 (pl) 2018-11-30
HK1210138A1 (en) 2016-04-15
AU2013343772A1 (en) 2015-03-19
JP6104397B2 (ja) 2017-03-29
WO2014072143A1 (de) 2014-05-15
PT2917179T (pt) 2018-10-11
US20150291520A1 (en) 2015-10-15
AU2013343772B2 (en) 2017-06-15
KR102158059B1 (ko) 2020-09-21
ZA201503136B (en) 2016-01-27
CA2890831C (en) 2020-04-21
BR112015007192B1 (pt) 2019-09-10

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